Piezoelectric film and method of manufacturing the piezoelectric film, ink jet head, method of forming image by the ink jet head, angular velocity sensor, method of measuring angular velocity by the angular velocity sensor, piezoelectric generating element, and method of generating electric power using the piezoelectric generating element

ABSTRACT

In order to provide a non-lead piezoelectric film having high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant, the present invention is a piezoelectric film comprising: a Na x M 1-x  layer  13  having a (001) orientation only; and a (1-α) (Bi, Na, Ba) TiO 3 -αBiQO 3  layer  15  having a (001) orientation only. The (1-α) (Bi, Na, Ba) TiO 3 -αBiQO 3  layer  15  is formed on the Na x M 1-x  layer  13 . M represents Pt, Ir, or PtIr. Q represents Fe, Co, Zn 0.5 Ti 0.5 , or Mg 0.5 Ti 0.5 . x represents a value of not less than 0.002 and not more than 0.02. α represents a value of not less than 0.20 and not more than 0.50.

This is a continuation of International Application No. PCT/JP2013/002426, with an international filing date of Apr. 10, 2013, which claims priority of Japanese Patent Application No. 2012-172636, filed on August 3, Japanese Patent Application No. 2012-172637, filed on August 3, Japanese Patent Application No. 2012-172638, filed on August 3, and Japanese Patent Application No. 2012-172639, filed on August 3, the contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a piezoelectric film comprising a piezoelectric layer and a method of manufacturing the piezoelectric film. The present invention further relates to an ink jet head comprising the piezoelectric film and a method of forming an image by the head, to an angular velocity sensor comprising the piezoelectric film and a method of measuring an angular velocity by the sensor, and to a piezoelectric generating element comprising the piezoelectric film and a method of generating electric power using the element.

2. Description of the Related Art

Perovskite composite oxide [(Bi, Na)_(1-β) Ba_(β)] TiO₃ (hereinafter, referred to as “NBT-BT”) has been recently researched and developed as a non-lead (lead-free) ferroelectric material.

Japanese Patent Publication No. Hei 4-60073B and T. Takenaka et al., Japanese Journal of Applied Physics, Vol. 30, No. 9B, (1991), pp. 2236-2239 disclose that a NBT-BT layer has high piezoelectric performance when the NBT-BT layer has a composition around the Morphotropic Phase Boundary (hereinafter, referred to as “MPB”) having a barium molar ratio β (=[Ba/(Bi+Na+Ba)]) of 3-15%.

Japanese Patent Publication No. 4140796B and E. V. Ramana et al., Solid State Sciences, Vol. 12, (2010), pp. 956-962 disclose (1-α)(Bi,Na,Ba)TiO₃-αBiFeO₃ where perovskite composite oxide NBT-BT is combined with perovskite oxide BiFeO₃. The piezoelectric performance of the (1-α)(Bi,Na,Ba)TiO₃-αBiFeO₃ is maintained even at a solder reflow temperature of 180 degrees Celsius.

The (1-α) (Bi, Na, Ba) TiO₃-αBiFeO₃ has also been expected as a non-lead ferroelectric material capable of being used instead of PZT. However, the (1-α) (Bi, Na, Ba) TiO₃-αBiFeO₃ has lower piezoelectric performance than the PZT.

A ferroelectric material containing (Bi, Na, Ba) TiO₃ or BiFeO₃ has high dielectric loss. When the dielectric loss is high, the ferroelectric performance and the piezoelectric performance are deteriorated significantly.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a non-lead piezoelectric film having high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

It is another object of the present invention to provide an ink jet head, an angular velocity sensor, and a piezoelectric generating element, each comprising the non-lead piezoelectric film. It is still another object of the present invention to provide a method of forming an image by this ink jet head, a method of measuring an angular velocity by this angular velocity sensor, and a method of generating electric power using this piezoelectric generating element.

The present invention provides a piezoelectric film comprising:

a Na_(x)M_(1-x) layer having a (001) orientation only; and

a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; wherein

the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer;

M represents Pt, Ir, or PtIr;

Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5);

x represents a value of not less than 0.002 and not more than 0.02; and

α represents a value of not less than 0.20 and not more than 0.50.

The spirit of the present invention includes an ink jet head, an angular velocity sensor, and a piezoelectric generating element, each of which comprises the piezoelectric film.

The spirit of the present invention includes a method of measuring an angular velocity by the angular velocity sensor, a method of forming an image by the ink jet head, and a method of generating electric power using the piezoelectric generating element.

The present invention provides a non-lead piezoelectric film having high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

The present invention provides an ink jet head comprising the non-lead piezoelectric film and a method of forming an image by the head.

The present invention provides an angular velocity sensor comprising the non-lead piezoelectric film and a method of measuring an angular velocity by the sensor.

The present invention provides a piezoelectric generating element comprising the non-lead piezoelectric film and a method of generating electric power using the element.

Other features, elements, processes, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the present invention with reference to the attached drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A shows a cross-sectional view of a piezoelectric film according to an embodiment.

FIG. 1B shows a variation of the piezoelectric film shown in FIG. 1A.

FIG. 2 shows an X-ray diffraction profile of the piezoelectric films according to the example A1—the example A3 and the comparative example A1—the example A2.

FIG. 3 shows an X-ray diffraction profile of the piezoelectric films according to the example A1, the example A4—the example A8, and the comparative example A3—the comparative example A4.

FIG. 4 shows an X-ray diffraction profile of the piezoelectric films according to the example A1, the example A9, and the example A10.

FIG. 5 shows P-E hysteresis curves of the piezoelectric films according to the example A1 and the comparative example A1.

FIG. 6 is a perspective view schematically showing an example of an ink jet head of the present invention and partially showing a cross section of the ink jet head.

FIG. 7 is an exploded perspective view schematically showing main parts including a pressure chamber member and an actuator part in the ink jet head shown in FIG. 6 and partially showing a cross section of the main parts.

FIG. 8 is a cross-sectional view schematically showing an example of the main parts including the pressure chamber member and the actuator part in the ink jet head shown in FIG. 6.

FIG. 9 is a perspective view schematically showing an example of an angular velocity sensor of the present invention.

FIG. 10 is a cross-sectional view showing a cross section E1 of the angular velocity sensor shown in FIG. 9.

FIG. 11 is a perspective view schematically showing an example of a piezoelectric generating element of the present invention.

FIG. 12 is a cross-sectional view showing a cross section F1 of the piezoelectric generating element shown in FIG. 11.

FIG. 13 shows an X-ray diffraction profile of the piezoelectric films according to the example B1—the example B3 and the comparative example B1—the example B2.

FIG. 14 shows an X-ray diffraction profile of the piezoelectric films according to the example B1, the example B4—the example B8, and the comparative example B3—the comparative example B4.

FIG. 15 shows an X-ray diffraction profile of the piezoelectric films according to the example B1, the example B9, and the example B10.

FIG. 16 shows P-E hysteresis curves of the piezoelectric films according to the example B1 and the comparative example B1.

FIG. 17 shows an X-ray diffraction profile of the piezoelectric films according to the example C1—the example C3 and the comparative example C1—the comparative example C2.

FIG. 18 shows an X-ray diffraction profile of the piezoelectric films according to the example C1, the example C4—the example C8, and the comparative example C3—the comparative example C4.

FIG. 19 shows an X-ray diffraction profile of the piezoelectric films according to the example C1, the example C9, and the example C10.

FIG. 20 shows P-E hysteresis curves of the piezoelectric films according to the example C1 and the comparative example C1.

FIG. 21 shows an X-ray diffraction profile of the piezoelectric films according to the example D1—the example D3 and the comparative example D1—the comparative example D2.

FIG. 22 shows an X-ray diffraction profile of the piezoelectric films according to the example D1, the example D4—the example D8, and the comparative example D3—the comparative example D4.

FIG. 23 shows an X-ray diffraction profile of the piezoelectric films according to the example D1, the example D9, and the example D10.

FIG. 24 shows P-E hysteresis curves of the piezoelectric films according to the example D1 and the comparative example D1.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention are described below with reference to the drawings. In the following description, the same reference numerals are used to designate the same elements and parts, and therefore the overlapping description thereof can be omitted.

DEFINITION OF TERM

The term used in the instant specification is defined as below.

The term “temperature Td” means the temperature at which a polarization included in the piezoelectric layer disappears completely by heating the piezoelectric layer. In other words, the piezoelectric layer completely loses its polarization at a temperature more than the temperature Td. The piezoelectric layer which does not have the polarization fails to serve as a piezoelectric layer. In view of the solder reflow, it is desirable that the temperature Td be not less than 180 degrees Celsius.

[Piezoelectric Film]

FIG. 1A shows a piezoelectric film according to an embodiment. A piezoelectric film 1 a shown in FIG. 1A has a multilayer structure 16 a. This multilayer structure 16 a comprises a Na_(x)M_(1-x) layer 13 having a (001) orientation only and a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 having a (001) orientation only. The character “M” represents Pt, Ir, or PtIr. The character “Q” represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5). The Na_(x)M_(1-x) layer 13 serves as a first electrode layer. The multilayer structure 16 a further comprises a second electrode layer 17. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is interposed between the first electrode layer 13 and the second electrode layer 17. The first electrode layer 13 and the second electrode layer 17 are used to apply a voltage to the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15.

The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 has a (001) orientation only. In other words, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 does not have an orientation other than a (001) orientation. For example, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 does not have a (110) orientation. See the comparative examples A1, A2, B1, B2, C1, C2, D1 and D2, which are described later.

Similarly, the Na_(x)M_(1-x) layer 13 has a (001) orientation only.

The character x represents a value of not less 0.002 and not more than 0.02. When the value of x is less than 0.002, the crystalline orientation, the polarization-disappear temperature, and the piezoelectric constant are low. Furthermore, the dielectric loss is high. See the comparative examples A1, B1, C1, D1, and D2, which are described later.

When the value of x is over 0.02, the crystalline orientation, the polarization-disappear temperature, and the piezoelectric constant are low. Furthermore, the dielectric loss is high. See the comparative examples A2, B2, C2, and D2, which are described later.

The value of α is not less than 0.20 and not more than 0.50. When the value of α is less than 0.20, the polarization-disappear temperature is low. See the comparative examples A3, B3, C3, and D3, which are described later.

When the value of α is over 0.50, the crystalline orientation, the polarization-disappear temperature, and the piezoelectric constant are low. Furthermore, the dielectric loss is high. See the comparative examples A4, B4, C4, and D4, which are described later.

It is desirable that these stacked layers be in contact with each other. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 serves as a piezoelectric layer. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 has a small leak current, high crystallinity, and a high (001) orientation. For this reason, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 has high polarization-disappear temperature, low dielectric loss, and high piezoelectric performance, although it does not contain lead. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 has piezoelectric performance similar to that of the PZT layer.

Typically, the Na_(x)M_(1-x) layer 13 can be formed by sputtering. The Na_(x)M_(1-x) layer 13 can also be formed by a thin film formation technique such as pulsed laser deposition (PLD), chemical vapor deposition (CVD), sol-gel processing, or aerosol deposition (AD).

The thickness of the Na_(x)M_(1-x) layer 13 is not limited. As one example, the Na_(x)M_(1-x) layer 13 has a thickness of not less than approximately 2 nanometers.

The thickness of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is also not limited. The thickness thereof is at least 0.5 micrometers but not more than 10 micrometers, for example.

The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 has a perovskite crystal structure represented by the chemical formula ABO₃. The A site is Bi, Na, and Ba. The B site is Ti and Q. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 may contain a minute amount of impurities. The impurities typically may be Li and K to substitute for Na, and Sr and Ca to substitute for Ba, in the A site. The impurities typically may be Zr to substitute for Ti in the B site. Examples of the other impurities may include Mn, Co, Al, Ga, Nb, and Ta. Some of these impurities can improve the crystallinity and piezoelectric performance of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15.

Typically, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 can be formed by sputtering. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 can also be formed by another thin film formation technique such as PLD, CVD, sol-gel processing, or AD.

An example of the material of the second electrode layer 17 is a metal having a low electric resistance. Other examples of the material of the second electrode layer 17 include oxide conductors such as NiO, RuO₂, IrO₃, SrRuO₃, and LaNiO₃. The second electrode layer 17 may be composed of two or more kinds of these materials.

A metal layer may be interposed between the second electrode layer 17 and the (Bi, Na)TiO₃—BaTiO₃ layer 15 to improve the adhesion therebetween. Examples of the material of the metal layer include titanium, tantalum, iron, cobalt, nickel, and chrome. Two or more kinds of metals may be used.

FIG. 1B shows a variation of the piezoelectric film shown in FIG. 1A. As shown in FIG. 1B, a multilayer structure 16 b further comprises a substrate 11. The Na_(x)M_(1-x) layer 13 is formed on the substrate 11.

Examples of the substrate 11 are described below:

a silicon substrate;

an oxide substrate having a sodium chloride structure such as a MgO substrate,

an oxide substrate having a perovskite-type structure such as a SrTiO₃ substrate, a LaAlO₃ substrate, or a NdGaO₃ substrate;

an oxide substrate having a corundum-type structure such as a Al₂O₃ substrate;

an oxide substrate having a spinel-type structure such as a MgAl₂O₄ substrate;

an oxide substrate having a rutile-type structure such as a TiO₂ substrate; and

an oxide substrate having a crystal structure of cubic system such as a (La, Sr) (Al, Ta) O₃ substrate or an yttria-stabilized zirconia (YSZ) substrate.

Desirably, a silicon monocrystalline substrate or a MgO monocrystalline substrate may be used.

An interlayer may be formed on the surface of the substrate 11 by an epitaxial growth method. An example of the material of the interlayer is yttria-stabilized zirconia (YSZ).

Other examples of the material of the interlayer are described below:

materials having a fluorite-type structure such as CeO₂,

materials having a sodium chloride structure such as MgO, BaO, SrO, TiN, and ZrN,

materials having a perovskite-type structure such as SrTiO₃, LaAlO₃, (La, Sr) MnO₃, and (La, Sr) CoO₃; and

materials having a spinel-type structure such as γ-Al₂O₃ and MgAl₂O₄.

Two or more kinds of these materials may be used. As one example, the substrate 11 may be a laminate of CeO₂/YSZ/Si.

A metal layer is interposed between the substrate 11 and the Na_(x)M_(1-x) layer 13 to improve the adhesion therebetween. Examples of the material of the metal layer include Ti, Ta, Fe, Co, Ni, and Cr. Ti is desirable.

Examples

The following examples describe the present invention in more detail.

The following examples are composed of the example A, the example B, the example C, and the example D.

In the example A, Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is Fe. The example A is composed of the example A1—the example A10 and the comparative example A1—the comparative example A4.

In the example B, Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is Co. The example B is composed of the example B1—the example B10 and the comparative example B1—the comparative example B4.

In the example C, Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is Zn_(0.5)Ti_(0.5). The example C is composed of the example C1—the example C10 and the comparative example C1—the comparative example C4.

In the example D, Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is Mg_(0.5)Ti_(0.5). The example D is composed of the example D1—the example D10 and the comparative example D1—the comparative example D4.

EXAMPLES Example A1

A piezoelectric film shown in FIG. 1B was prepared as below.

First, a Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 having a (001) orientation only was formed on a MgO (100) monocrystalline substrate 11 by a sputtering method. The Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 had a thickness of 250 nanometers. The condition of the sputtering method is described below:

Target: Same composition as above

Gas atmosphere: Argon

RF power: 15 W

Substrate temperature: 300 degrees Celsius

The formed Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 was subjected to an X-ray diffraction analysis (XRD). As a result, it was observed that the Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 had a (001) orientation only.

The composition of the Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 was analyzed by an energy dispersive X-ray spectroscopy (SEM-EDX). It was confirmed that the composition of Na and Pt contained in the Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 was the same as the composition of the target.

The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 having a (001) orientation only was formed on the Na_(x)M_(1-x) (x=0.01, M=Pt) layer 13 by RF magnetron sputtering. In the example A1, Q was Fe. In the example A1, α was 0.2. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 had a thickness of 2.7 micrometers. This (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 had a composition around MPB.

The condition of the sputtering method of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is described below.

Target: Same composition as above

Atmosphere: Mixed gas of argon and oxygen (Flow ratio of Ar/O₂:50/50)

RF power: 170 W

Substrate temperature: 650 degrees Celsius

The formed (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was subjected to an X-ray diffraction analysis to analyze the crystal structure thereof. The X-ray diffraction analysis was carried out in such a manner that an X-ray beam was made incident from above the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15. FIG. 2 shows the result thereof. In the following examples and the comparative examples below, X-ray diffraction analyses were carried out in the same manner.

FIG. 2, FIG. 3, and FIG. 4 show the results of the X-ray diffraction profile. Observed was only the reflection peak derived from the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 having a (001) orientation only, except for the reflection peaks derived from the MgO (100) monocrystalline substrate 11 and the Na_(x)M_(1-x) layer 13. The intensity of the (001) reflection peak was 119,154 cps, which was a very high level. The profile shown in FIG. 2 means that the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 according to the example A1 has a significantly high (001) orientation.

Then, a gold layer (thickness: 100 nanometers) was formed by evaporation on the surface of the (1-α) (Bi, Na, Ba)TiO₃-αBiQO₃ layer 15. This gold layer served as the conductive layer 17. In this way, the piezoelectric film according to the example A1 was fabricated.

Using a platinum layer and the gold layer, the ferroelectric performance and the piezoelectric performance of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 were evaluated. FIG. 5 shows a P-E hysteresis curve of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 according to the example A1.

As shown in FIG. 5, it was confirmed that the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 exhibited better ferroelectric performance with an increase in the voltage applied to the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15. An impedance analyzer was used to measure the dielectric loss (hereinafter, referred to as “tan δ”) at 1 kHz. As a result, the value of tan δ of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was 2.8%. This means that the leak current of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is small.

The polarization-disappear temperature, namely, the temperature Td, of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was measured as below.

The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was set in a thermostatic oven. The P-E hysteresis curve of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was measured with an increase in temperature.

The temperature Td was measured in accordance with Journal of the American Ceramic Society 93 [4] (2010) 1108-1113.

The temperature Td of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 according to the example A1 was a high value of 188 degrees Celsius. This means that the piezoelectric performance of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 is maintained under a solder reflow temperature (180 degrees Celsius).

The piezoelectric performance of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was evaluated in the following manner. The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was cut into a strip with a width of 2 mm and worked into a cantilever shape. A potential difference was applied between the platinum layer and the gold layer, and the cantilever was displaced by the electric field generated between the two layers. The resulting displacement of the cantilever was measured with a laser displacement meter.

These results are shown in Table 1 and Table 2.

Example A2

An example similar to the example A1 was conducted, except that x=0.002. The results are shown in Table 1 and Table 2.

Example A3

An example similar to the example A1 was conducted, except that x=0.02. The results are shown in Table 1 and Table 2.

Example A4

An example similar to the example A1 was conducted, except that α=0.3. The results are shown in Table 1 and Table 2.

Example A5

An example similar to the example A1 was conducted, except that α=0.4. The results are shown in Table 1 and Table 2.

Example A6

An example similar to the example A1 was conducted, except that α=0.5. The results are shown in Table 1 and Table 2.

Example A7

An example similar to the example A1 was conducted, except that x=0.002 and α=0.5. The results are shown in Table 1 and Table 2.

Example A8

An example similar to the example A1 was conducted, except that x=0.02 and α=0.5. The results are shown in Table 1 and Table 2.

Example A9

An example similar to the example A1 was conducted, except that M=Ir. The results are shown in Table 1 and Table 2.

Example A10

An example similar to the example A1 was conducted, except that M=Ir_(0.5)Pt_(0.5). The results are shown in Table 1 and Table 2.

Comparative Example A1

An example similar to the example A1 was conducted, except that x=0.

Similarly, the present inventors tried the evaluation of the ferroelectric performance and the piezoelectric performance of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 in the comparative example A1. However, it was difficult to measure the P-E hysteresis curve accurately, since the leak current in the piezoelectric film was very high (see FIG. 5).

The (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 according to the comparative example A1 had a tan δ of 36%. It was difficult to measure the accurate temperature Td and the accurate piezoelectric constant d₃₁, since the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 of the comparative example A1 had such a high leak current. The estimated temperature Td was approximately 152 degrees Celsius.

Comparative Example A2

An example similar to the example A1 was conducted, except that x=0.05.

The reflection peak derived from the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 having a (001) orientation was also observed in the comparative example A2. However, another reflection peak derived from another crystalline orientation (110) included in the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 was also observed.

Comparative Example A3

An example similar to the example A1 was conducted, except that α=0.1.

Comparative Example A4

An example similar to the example A1 was conducted, except that α=0.6.

TABLE 1 Q = Fe (001) Peak Orientation intensity M x α direction (cps) Example A1 Pt 0.01 0.20 only (001) 119,154 Example A2 Pt 0.002 0.20 only (001) 79,088 Example A3 Pt 0.02 0.20 only (001) 85,365 Example A4 Pt 0.01 0.30 only (001) 115,840 Example A5 Pt 0.01 0.40 only (001) 109,883 Example A6 Pt 0.01 0.50 only (001) 96,060 Example A7 Pt 0.002 0.50 only (001) 65,618 Example A8 Pt 0.02 0.50 only (001) 69,360 Example A9 Ir 0.01 0.20 only (001) 95,354 Example A10 Pt_(0.5)Ir_(0.5) 0.01 0.20 only (001) 107,201 Comparative Pt 0 0.20 (001) and (110) 26,452 example A1 Comparative Pt 0.05 0.20 (001) and (110) 41,163 example A2 Comparative Pt 0.01 0.10 only (001) 126,327 example A3 Comparative Pt 0.01 0.60 only (001) 39,719 example A4

TABLE 2 Q = Fe Polarization-disappear Piezoelectric Dielectric loss temperature Td constant (tan δ) (degree Celsius) d31 Example A1 2.8% 188 −106 pC/N  Example A2 4.0% 185 −87 pC/N Example A3 4.3% 186 −90 pC/N Example A4 3.2% 209 −103 pC/N  Example A5 3.6% 228 −98 pC/N Example A6 4.0% 251 −96 pC/N Example A7 5.2% 226 −84 pC/N Example A8 5.6% 223 −87 pC/N Example A9 2.8% 188 −106 pC/N  Example A10 2.8% 188 −102 pC/N  Comparative  36% 152 −35 pC/N example A1 Comparative  18% 160 −61 pC/N example A2 Comparative 2.7% 138 −97 pC/N example A3 Comparative  22% 171 −58 pC/N example A4

As is clear from Table 1 and Table 2, if both of the following items (a) and (b) are satisfied, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 (Q=Fe) has high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

(a) the value of x is not less than 0.002 and not more than 0.02.

(b) the value of α is not less than 0.2 and not more than 0.5.

As is clear from the example A2, the example A7, and the comparative example A1, it is necessary that the value of x is not less than 0.002.

As is clear from the example A3, the example A8, and the comparative example A2, it is necessary that the value of x is not more than 0.02.

As is clear from the example A1, the example A2, the example A3, and the comparative example A3, it is necessary that the value of α is not less than 0.2.

As is clear from the example A6, the example A7, the example A8, and the comparative example A4, it is necessary that the value of α is not more than 0.5.

Example B

An example similar to the example A was conducted, except that Co was used instead of Fe as Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15. Table 3 and Table 4 show the results of the example B, which is composed of the example B1—the example B10 and the comparative example B1—the comparative example B4. FIG. 13-FIG. 16 correspond to FIG. 2-FIG. 5, respectively.

TABLE 3 Q = Co (001) Peak Orientation intensity M x α direction (cps) Example B1 Pt 0.01 0.20 only (001) 110,881 Example B2 Pt 0.002 0.20 only (001) 73,154 Example B3 Pt 0.02 0.20 only (001) 79,397 Example B4 Pt 0.01 0.30 only (001) 107,317 Example B5 Pt 0.01 0.40 only (001) 102,915 Example B6 Pt 0.01 0.50 only (001) 90,104 Example B7 Pt 0.002 0.50 only (001) 63,223 Example B8 Pt 0.02 0.50 only (001) 65,956 Example B9 Ir 0.01 0.20 only (001) 89,98 Example B10 Pt_(0.5)Ir_(0.5) 0.01 0.20 only (001) 97,695 Comparative Pt 0 0.20 (001) and (110) 24,061 example B1 Comparative Pt 0.05 0.20 (001) and (110) 38,183 example B2 Comparative Pt 0.01 0.10 only (001) 117,357 example B3 Comparative Pt 0.01 0.60 only (001) 36,389 example B4

TABLE 4 Q = Co Polarization-disappear Piezoelectric Dielectric loss temperature Td constant (tan δ) (degree Celsius) d31 Example B1 3.4% 190 −104 pC/N  Example B2 4.8% 187 −85 pC/N Example B3 5.2% 188 −88 pC/N Example B4 3.8% 211 −101 pC/N  Example B5 4.2% 230 −96 pC/N Example B6 4.7% 253 −94 pC/N Example B7 6.1% 228 −82 pC/N Example B8 6.5% 225 −85 pC/N Example B9 3.5% 189 −97 pC/N Example B10 3.4% 190 −99 pC/N Comparative  43% 154 −34 pC/N example B1 Comparative  22% 161 −60 pC/N example B2 Comparative 3.2% 139 −95 pC/N example B3 Comparative  26% 172 −57 pC/N example B4

Similarly to the example A, as is clear from Table 3 and Table 4, if both of the following items (a) and (b) are satisfied, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 (Q=Co) has high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

(a) the value of x is not less than 0.002 and not more than 0.02.

(b) the value of α is not less than 0.2 and not more than 0.5.

Example C

An example similar to the example A was conducted, except that Zn_(0.5)Ti_(0.5) was used instead of Fe as Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15. Table 5 and Table 6 show the results of the example C, which is composed of the example C1—the example C10 and the comparative example C1—the comparative example C4. FIG. 17-FIG. 20 correspond to FIG. 2-FIG. 5, respectively.

TABLE 5 Q = Zn_(0.5)Ti_(0.5) (001) Peak Orientation intensity M x α direction (cps) Example C1 Pt 0.01 0.20 only (001) 116,707 Example C2 Pt 0.002 0.20 only (001) 77,065 Example C3 Pt 0.02 0.20 only (001) 83,552 Example C4 Pt 0.01 0.30 only (001) 113,658 Example C5 Pt 0.01 0.40 only (001) 108,698 Example C6 Pt 0.01 0.50 only (001) 94,361 Example C7 Pt 0.002 0.50 only (001) 64,509 Example C8 Pt 0.02 0.50 only (001) 67,742 Example C9 Ir 0.01 0.20 only (001) 93,645 Example C10 Pt_(0.5)Ir_(0.5) 0.01 0.20 only (001) 105,506 Comparative Pt 0 0.20 (001) and (110) 25,832 example C1 Comparative Pt 0.05 0.20 (001) and (110) 40,339 example C2 Comparative Pt 0.01 0.10 only (001) 123,258 example C3 Comparative Pt 0.01 0.60 only (001) 38,933 example C4

TABLE 6 Q = Zn_(0.5)Ti_(0.5) Polarization-disappear Piezoelectric Dielectric loss temperature Td constant (tan δ) (degree Celsius) d31 Example C1 2.5% 189 −105 pC/N  Example C2 3.5% 186 −86 pC/N Example C3 3.8% 187 −89 pC/N Example C4 2.8% 210 −102 pC/N  Example C5 3.1% 229 −97 pC/N Example C6 3.5% 251 −95 pC/N Example C7 4.6% 226 −83 pC/N Example C8 4.9% 224 −86 pC/N Example C9 2.6% 188 −98 pC/N Example C10 2.5% 188 −101 pC/N  Comparative  32% 153 −35 pC/N example C1 Comparative  16% 161 −60 pC/N example C2 Comparative 2.3% 139 −96 pC/N example C3 Comparative  20% 171 −57 pC/N example C4

Similarly to the example A, as is clear from Table 5 and Table 6, if both of the following items (a) and (b) are satisfied, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 (Q=Zn_(0.5)Ti_(0.5)) has high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

(a) the value of x is not less than 0.002 and not more than 0.02.

(b) the value of α is not less than 0.2 and not more than 0.5.

Example D

An example similar to the example A was conducted, except that Mg_(0.5)Ti_(0.5) was used instead of Fe as Q of the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15. Table 7 and Table 8 show the results of the example D, which is composed of the example D1—the example D10 and the comparative example D1—the comparative example D4. FIG. 21-FIG. 24 correspond to FIG. 2-FIG. 5, respectively.

TABLE 7 Q = Mg_(0.5)Ti_(0.5) (001) Peak Orientation intensity M x α direction (cps) Example D1 Pt 0.01 0.20 only (001) 114,984 Example D2 Pt 0.002 0.20 only (001) 76,398 Example D3 Pt 0.02 0.20 only (001) 81,901 Example D4 Pt 0.01 0.30 only (001) 112,128 Example D5 Pt 0.01 0.40 only (001) 106,356 Example D6 Pt 0.01 0.50 only (001) 92,730 Example D7 Pt 0.002 0.50 only (001) 63,696 Example D8 Pt 0.02 0.50 only (001) 67,259 Example D9 Ir 0.01 0.20 only (001) 92,355 Example D10 Pt_(0.5)Ir_(0.5) 0.01 0.20 only (001) 103,231 Comparative Pt 0 0.20 (001) and (110) 25,131 example D1 Comparative Pt 0.05 0.20 (001) and (110) 39,108 example D2 Comparative Pt 0.01 0.10 only (001) 121,852 example D3 Comparative Pt 0.01 0.60 only (001) 67,259 example D4

TABLE 8 Q = Mg_(0.5)Ti_(0.5) Polarization-disappear Piezoelectric Dielectric loss temperature Td constant (tan δ) (degree Celsius) d31 Example D1 2.5% 189 −105 pC/N  Example D2 3.6% 186 −87 pC/N Example D3 3.9% 187 −89 pC/N Example D4 2.9% 211 −102 pC/N  Example D5 3.2% 230 −98 pC/N Example D6 3.6% 252 −96 pC/N Example D7 4.6% 227 −83 pC/N Example D8 5.0% 225 −87 pC/N Example D9 2.6% 188 −99 pC/N Example D10 2.5% 189 −101 pC/N  Comparative  32% 153 −35 pC/N example D1 Comparative  16% 161 −61 pC/N example D2 Comparative 2.4% 139 −97 pC/N example D3 Comparative  19% 171 −58 pC/N example D4

Similarly to the example A, as is clear from Table 7 and Table 8, if both of the following items (a) and (b) are satisfied, the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 (Q=Mg_(0.5)Ti_(0.5)) has high crystalline orientation, low dielectric loss, high polarization-disappear temperature, and high piezoelectric constant.

(a) the value of x is not less than 0.002 and not more than 0.02.

(b) the value of α is not less than 0.2 and not more than 0.5.

The ink jet head, the angular velocity sensor, and the piezoelectric generating element of the present invention each comprising the above-mentioned piezoelectric film are described. For more detail, see International publication No. 2010/047049. U.S. Pat. No. 7,870,787 and Chinese Laid-open patent application publication No. 101981718 are the United States patent publication and the Chinese laid-open patent application publication which correspond to International publication No. 2010/047049, respectively.

[Ink Jet Head]

An ink jet head of the present invention will be described below with reference to FIG. 6 to FIG. 8.

FIG. 6 shows one embodiment of the ink jet head of the present invention. FIG. 7 is an exploded view showing main parts including a pressure chamber member and an actuator part in an ink jet head 100 shown in FIG. 6.

A reference character A in FIG. 6 and FIG. 7 indicates a pressure chamber member. The pressure chamber member A includes through-holes 101 that penetrate therethrough in its thickness direction (in the vertical direction in these diagrams). The through-hole 101 shown in FIG. 7 is a part of the through-hole 101 in the cross section in the thickness direction of the pressure chamber member A. A reference character B indicates an actuator part including piezoelectric films and vibration layers. A reference character C indicates an ink passage member C including common liquid chambers 105 and ink passages 107. The pressure chamber member A, the actuator part B, and the ink passage member C are bonded to each other so that the pressure chamber member A is sandwiched between the actuator part B and the ink passage member C. When the pressure chamber member A, the actuator part B, and the ink passage member C are bonded to each other, each of the through-holes 101 forms a pressure chamber 102 for storing ink supplied from the common liquid chamber 105.

The actuator part B has piezoelectric films and vibration layers that are aligned over the corresponding pressure chambers 102 respectively in plan view. In FIG. 6 and FIG. 7, a reference numeral 103 indicates an individual electrode layer that is a part of the piezoelectric film. As shown in FIG. 6, in the ink jet head 100, a plurality of individual electrode layers 103, that is, piezoelectric films are arranged in a zigzag pattern in plan view.

The ink passage member C has a plurality of common liquid chambers 105 arranged in stripes in plan view. In FIG. 6 and FIG. 7, each of the common liquid chambers 105 is aligned over a plurality of pressure chambers 102 in plan view. The common liquid chambers 105 extend in the ink supply direction (in the direction indicated by arrows in FIG. 6) in the ink jet head 100. The ink passage member C has supply ports 106, each of which supplies the ink in the common liquid chamber 105 to one of the pressure chambers 102, and ink passages 107, each of which ejects the ink in the corresponding pressure chamber 102 through a corresponding nozzle hole 108. Usually, one pressure chamber 102 has one supply port 106 and one nozzle hole 108. The nozzle holes 108 are formed in a nozzle plate D. The nozzle plate D is bonded to the ink passage member C so that the nozzle plate D and the pressure chamber member A sandwich the ink passage member C therebetween.

In FIG. 6, a reference character E indicates an IC chip. The IC chip E is connected electrically to the individual electrode layers 103, which are exposed on the surface of the actuator part B, through bonding wires BW. For simplicity of FIG. 6, only a part of the bonding wires BW are shown in FIG. 6.

FIG. 7 shows the configuration of the main parts including the pressure chamber member A and the actuator part B. FIG. 8 shows the cross section perpendicular to the ink supply direction (in the direction indicated by the arrows in FIG. 6) in the pressure chamber member A and the actuator part B. The actuator part B includes piezoelectric films 104 (104 a to 104 d) each having the piezoelectric layer 15 sandwiched between the first electrode (the individual electrode layer 103) and the second electrode (the common electrode layer 112). The individual electrode layers 103 correspond one to one to the piezoelectric films 104 a to 104 d. The common electrode layer 112 is a single layer electrode that is common to the piezoelectric films 104 a to 104 d.

As surrounded by the dashed-line in FIG. 8, the above-mentioned piezoelectric films 104 are arranged in the ink jet head. The piezoelectric film is the piezoelectric film described in the item titled as “Piezoelectric film”.

[Image Forming Method by Ink Jet Head]

The image forming method of the present invention includes, in the above-described ink jet head of the present invention, a step of applying a voltage to the piezoelectric layer through the first and second electrodes (that is, the individual electrode layer and the common electrode layer) to displace, based on the piezoelectric effect, the vibration layer in its film thickness direction so that the volumetric capacity of the pressure chamber changes; and a step of ejecting the ink from the pressure chamber by the displacement.

The voltage to be applied to the piezoelectric layer is changed with the relative position between the ink jet head and an object like a sheet of paper, on which an image is to be formed, being changed, so as to control the timing of ink ejection from the ink jet head and the amount of ink ejected therefrom. As a result, an image is formed on the surface of the object. The term “image” used in the present description includes a character. In other words, according to the present method of forming an image, a letter, a picture, or a figure is printed to a print target such as a sheet of paper. With this method, a picturesque image can be printed.

[Angular Velocity Sensor]

FIG. 9 shows an example of an angular velocity sensor of the present invention. FIG. 10 shows a cross section E1 of an angular velocity sensor 21 a shown in FIG. 9. The angular velocity sensor 21 a shown in FIG. 9 is a so-called tuning-fork type angular velocity sensor. This type of angular velocity sensor can be used in a navigation apparatus for a vehicle, and as a sensor for correcting image blurring due to hand movement in a digital still camera.

The angular velocity sensor 21 a shown in FIG. 9 comprises a substrate 200 having vibration parts 200 b and piezoelectric films 208 bonded to the vibration parts 200 b.

The substrate 200 has a stationary part 200 a and a pair of arms (vibration parts 200 b) extending in a predetermined direction from the stationary part 200 a. The direction in which the vibration parts 200 b extend is the same as the direction in which the central axis of rotation L of the angular velocity detected by the angular velocity sensor 21 extends. More specifically, it is the Y direction in FIG. 9. The substrate 200 has a shape of a tuning fork including two arms (vibration parts 200 b), when viewed from the thickness direction of the substrate 200 (the Z direction in FIG. 9).

The material of the substrate 200 is not limited. The material is, for example, Si, glass, ceramic, or metal. A monocrystalline Si substrate can be used as the substrate 200. The thickness of the substrate 200 is not limited as long as the functions of the angular velocity sensor 21 a can develop. More particularly, the substrate 200 has a thickness of at least 0.1 mm but not more than 0.8 mm. The thickness of the stationary part 200 a can be different from that of the vibration part 200 b.

The piezoelectric film 208 is bonded to the vibration part 200 b. The piezoelectric film 208 is the piezoelectric film described in the item titled as “Piezoelectric film”. As shown in FIG. 9 and FIG. 10, the piezoelectric film 208 comprises the first electrode 13 (202), the piezoelectric layer 15, and the second electrode layer 17 (205).

The second electrode 205 has an electrode group including a drive electrode 206 and a sense electrode 207. The drive electrode 206 applies a driving voltage that oscillates the vibration part 200 b to the piezoelectric layer 15. The sense electrode 207 measures a deformation of the vibration part 200 b caused by an angular velocity applied to the vibration part 200 b. That is, the vibration part 200 b usually oscillates in the width direction thereof (the X direction in FIG. 9). More particularly, in the angular velocity sensor shown in FIG. 9, a pair of drive electrodes 206 are provided on both of the width-direction edge portions of the vibration part 200 b along the length direction thereof (the Y direction in FIG. 9). Only one drive electrode 206 may be provided on one of the width-direction edge portions of the vibration part 200 b. In the angular velocity sensor shown in FIG. 9, the sense electrode 207 is provided along the length direction of the vibration part 200 b and sandwiched between the pair of drive electrodes 206. A plurality of sense electrodes 207 may be provided on the vibration part 200 b. The deformation of the vibration part 200 b measured by the sense electrode 207 usually is a deflection in the thickness direction thereof (the Z direction in FIG. 9).

In the angular velocity sensor of the present invention, one of the first electrode and the second electrode selected therefrom can be composed of an electrode group including the drive electrode and the sense electrode. In the angular velocity sensor 21 a shown in FIG. 9, the second electrode 205 is composed of the electrode group. Unlike this angular velocity sensor, the first electrode 202 can be composed of the electrode group.

The first electrode 202, the drive electrode 206, and the sense electrode 207 have connection terminals 202 a, 206 a, and 207 a, respectively, formed at the end portions thereof. The shape and position of each of the connection terminals are not limited. In FIG. 9, the connection terminals are provided on the stationary part 200 a.

In the angular velocity sensor shown in FIG. 9, the piezoelectric film 208 is bonded to both the vibration part 200 b and the stationary part 200 a. The bonding state of the piezoelectric film 208 is not limited as long as the piezoelectric film 208 can oscillate the vibration part 200 b and measure the deformation of the vibration part 200 b. For example, the piezoelectric film 208 may be bonded only to the vibration part 200 b.

The angular velocity sensor of the present invention may have two or more vibration part groups each consisting of a pair of vibration parts 200 b. Such an angular velocity sensor can serve as a biaxial or triaxial angular velocity sensor capable of measuring angular velocities with respect to a plurality of central axes of rotation. The angular velocity sensor shown in FIG. 9 has one vibration part group consisting of a pair of vibration parts 200 b.

[Method of Measuring Angular Velocity By Angular Velocity Sensor]

The angular velocity measuring method of the present invention uses the angular velocity sensor of the present invention, and includes the steps of: applying a driving voltage to the piezoelectric layer to oscillate the vibration part of the substrate; and measuring a deformation of the vibration part caused by an angular velocity applied to the oscillating vibration part to obtain a value of the applied angular velocity. The driving voltage is applied between the drive electrode and one of the first electrode and the second electrode (the other electrode) that serves neither as the drive electrode nor as the sense electrode, and thus the driving voltage is applied to the piezoelectric layer. The sense electrode and the other electrode measure the deformation of the oscillating vibration part caused by the angular velocity.

Hereinafter, the angular velocity measuring method by the angular velocity sensor 21 a shown in FIG. 9 is described. A driving voltage having a frequency that resonates with the natural vibration of the vibration part 200 b is applied to the piezoelectric layer 15 through the first electrode 202 and the drive electrode 206 so as to oscillate the vibration part 200 b. The driving voltage can be applied, for example, by grounding the first electrode 202 and changing the potential of the drive electrode 206 (in other words, the driving voltage is the potential difference between the first electrode 202 and the drive electrode 206). The angular velocity sensor 21 a includes a pair of vibration parts 200 b that are arranged in the form of the tuning fork. Usually, reverse (positive and negative) voltages are applied to the drive electrodes 206 provided on the respective vibration parts 200 b of the pair. This allows the respective vibration parts 200 b to oscillate in the mode in which they vibrate in the directions opposite to each other (the mode in which they vibrate symmetrically with respect to the central axis of rotation L shown in FIG. 9). In the angular velocity sensors 21 a shown in FIG. 9, the vibration parts 200 b oscillate in their width direction (the X direction). The angular velocity can be measured by oscillating only one of the pair of vibration parts 200 b. For accurate measurement, however, it is preferable to oscillate both of the vibration parts 200 b in the mode in which they vibrate in the directions opposite to each other.

When an angular velocity ω with respect to the central axis of rotation L is applied to the angular velocity sensor 21 a in which the vibration parts 200 b are oscillating, the vibration parts 200 b are deflected respectively in their thickness direction (the Z direction) by Coriolis force. In the case where the respective vibration parts 200 b are oscillating in the opposite direction mode, they are deflected in the opposite directions by the same degree. The piezoelectric layer 15 bonded to the vibration part 200 b is also deflected according to this deflection of the vibration part 200 b. As a result, a potential difference is generated between the first electrode 202 and the sense electrode 207 in accordance with the deflection of the piezoelectric layer 15, that is, the magnitude of the generated Coriolis force. The angular velocity ω applied to the angular velocity sensor 21 a can be measured by measuring the magnitude of the potential difference.

The following relationship between a Coriolis force Fc and the angular velocity ω is true:

Fc=2mvω

where v is the velocity of the oscillating vibration part 200 b in the oscillation direction, and m is the mass of the vibration part 200 b. As shown in this equation, the angular velocity ω can be calculated from the Coriolis force Fc.

[Piezoelectric Generating Element]

FIG. 11 shows an example of the piezoelectric generating element of the present invention. FIG. 12 shows a cross section F1 of a piezoelectric generating element 22 a shown in FIG. 11. The piezoelectric generating elements 22 a are elements that convert externally-applied mechanical vibration into electrical energy. The piezoelectric generating elements 22 a are applied suitably to a self-sustained power supply for generating electric power from various vibrations including engine vibrations and driving vibrations generated in vehicles and machines, and vibrations generated during walking.

The piezoelectric generating element 22 a shown in FIG. 11 comprises a substrate 300 having a vibration part 300 b and a piezoelectric film 308 bonded to the vibration part 300 b.

The substrate 300 has a stationary part 300 a, and a vibration part 300 b having a beam extending in a predetermined direction from the stationary part 300 a. The material of the stationary part 300 a can be the same as the material of the vibration part 300 b. These materials may, however, be different from each other. The stationary part 300 a and the vibration part 300 b made of materials different from each other may be bonded to each other.

The material of the substrate 300 is not limited. The material is, for example, Si, glass, ceramic, or metal. A monocrystalline Si substrate can be used as the substrate 300. The substrate 300 has a thickness of, for example, at least 0.1 mm but not more than 0.8 mm. The stationary part 300 a may have a thickness different from that of the vibration part 300 b. The thickness of the vibration part 300 b can be adjusted for efficient power generation by changing the resonance frequency of the vibration part 300 b.

A weight load 306 is bonded to the vibration part 300 b. The weight load 306 adjusts the resonance frequency of the vibration part 300 b. The weight load 306 is, for example, a vapor-deposited thin film of Ni. The material, shape, and mass of the weight load 306, as well as the position to which the weight load 306 is bonded can be adjusted according to a desired resonance frequency of the vibration part 300 b. The weight load 306 may be omitted. The weight load 306 is not necessary when the resonance frequency of the vibration part 300 b is not adjusted.

The piezoelectric film 308 is bonded to the vibration part 300 b. The piezoelectric film 308 is the piezoelectric film described in the item titled as “Piezoelectric film”. As shown in FIG. 11 and FIG. 12, the piezoelectric film 308 comprises the first electrode 13 (302), the piezoelectric layer 15, and the second electrode 17 (305).

In the piezoelectric generating element shown in FIG. 11, a part of the first electrode 302 is exposed. This part can serve as a connection terminal 302 a.

In the piezoelectric generating element shown in FIG. 11, the piezoelectric film 308 can be bonded to both of the vibration part 300 b and the stationary part 300 a. The piezoelectric film 308 can be bonded only to the vibration part 300 b.

When the piezoelectric generating element of the present invention has a plurality of vibration parts 300 b, an increased amount of electric power can be generated. Such a piezoelectric generating element can be applied to mechanical vibrations containing a wide range of frequency components if the plurality of vibration parts 300 b have different resonance frequencies.

[Method of Generating Electric Power Using Piezoelectric Generating Element]

The above-described piezoelectric generating element of the present invention is vibrated to obtain electric power through the first electrode and the second electrode.

When mechanical vibration is applied externally to the piezoelectric generating element 22 a, the vibration part 300 b starts vibrating to produce vertical deflection with respect to the stationary part 300 a. The piezoelectric effect produced by this vibration generates an electromotive force across the piezoelectric layer 15. As a result, a potential difference is generated between the first electrode 302 and the second electrode 305 that sandwich the piezoelectric layer 15 therebetween. The higher piezoelectric performance of the piezoelectric layer 15 generates a larger potential difference between the first and second electrodes. Particularly in the case where the resonance frequency of the vibration part 300 b is close to the frequency of mechanical vibration to be applied externally to the element, the amplitude of the vibration part 300 b increases and thus the electric power generation characteristics are improved. Therefore, the weight load 306 is preferably used to adjust the resonance frequency of the vibration part 300 b to be close to the frequency of mechanical vibration applied externally to the element.

INDUSTRIAL APPLICABILITY

A piezoelectric film comprising the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer 15 can be used for an ink jet head, an angular velocity sensor and a piezoelectric generating element.

While the present invention has been described with respect to preferred embodiments thereof, it will be apparent to those skilled in the art that the disclosed invention may be modified in numerous ways and may assume many embodiments other than those specifically described above. Accordingly, it is intended by the appended claims to cover all modifications of the invention that fall within the true spirit and scope of the invention.

REFERENCE SIGNS LIST

-   11: substrate -   13: Na_(x)M_(1-x) layer (first electrode) -   15: (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer -   17: conductive layer (second electrode) 

1. A piezoelectric film comprising: a Na_(x)M_(1-x) layer having a (001) orientation only; and a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; and α represents a value of not less than 0.20 and not more than 0.50.
 2. The piezoelectric film according to claim 1, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 3. The piezoelectric film according to claim 1, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 4. An ink jet head comprising: a piezoelectric film having a piezoelectric layer sandwiched between a first electrode and a second electrode; a vibration layer bonded to the piezoelectric film; and a pressure chamber member having a pressure chamber for storing ink and bonded to a surface of the vibration layer opposite to a surface to which the piezoelectric film is bonded; wherein the vibration layer is bonded to the piezoelectric film so that the vibration layer is displaceable in its film thickness direction according to a displacement of the piezoelectric film based on a piezoelectric effect; the vibration layer and the pressure chamber member are bonded to each other so that a volumetric capacity of the pressure chamber changes according to a displacement of the vibration layer and so that the ink in the pressure chamber is ejected according to a change in the volumetric capacity of the pressure chamber; the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; and α represents a value of not less than 0.20 and not more than 0.50.
 5. The ink jet head according to claim 4, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 6. The ink jet head according to claim 4, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 7. A method of forming an image by an ink jet head, the method comprising: a step (a) of preparing the ink jet head, wherein the ink jet head comprises: a piezoelectric film having a piezoelectric layer sandwiched between a first electrode and a second electrode; a vibration layer bonded to the piezoelectric film; and a pressure chamber member having a pressure chamber for storing ink and bonded to a surface of the vibration layer opposite to a surface to which the piezoelectric film is bonded, the vibration layer is bonded to the piezoelectric film so that the vibration layer is displaceable in its film thickness direction according to a displacement of the piezoelectric film based on a piezoelectric effect, the vibration layer and the pressure chamber member are bonded to each other so that a volumetric capacity of the pressure chamber changes according to a displacement of the vibration layer and so that the ink in the pressure chamber is ejected according to a change in the volumetric capacity of the pressure chamber, the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; and α represents a value of not less than 0.20 and not more than 0.50; a step (b) of applying a voltage to the piezoelectric layer through the first electrode and the second electrode to displace, based on the piezoelectric effect, the vibration layer in its film thickness direction so that the volumetric capacity of the pressure chamber changes and eject the ink from the pressure chamber by the displacement.
 8. The method according to claim 7, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 9. The method according to claim 7, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 10. An angular velocity sensor comprising: a substrate having a vibration part; and a piezoelectric film bonded to the vibration part and having a piezoelectric layer sandwiched between a first electrode and a second electrode, wherein the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; α represents a value of not less than 0.20 and not more than 0.50; and one of the first electrode and the second electrode selected therefrom is composed of an electrode group including a drive electrode for applying a driving voltage that oscillates the vibration part to the piezoelectric layer and a sense electrode for measuring a displacement of the vibration part caused by an angular velocity applied to the oscillating vibration part.
 11. The angular velocity sensor according to claim 10, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 12. The angular velocity sensor according to claim 10, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 13. A method of measuring an angular velocity by an angular velocity sensor, the method comprising: a step (a) of preparing the angular velocity sensor, wherein the angular velocity sensor comprises: a substrate having a vibration part; and a piezoelectric film bonded to the vibration part and having a piezoelectric layer sandwiched between a first electrode and a second electrode, the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; α represents a value of not less than 0.20 and not more than 0.50; and one of the first electrode and the second electrode selected therefrom is composed of an electrode group including a drive electrode and a sense electrode; a step (b) of applying a driving voltage to the piezoelectric layer through the drive electrode and the other of the first electrode and the second electrode selected therefrom to oscillate the vibration part; and a step (c) of measuring, through the other electrode and the sense electrode, a displacement of the vibration part caused by an angular velocity applied to the oscillating vibration part to obtain a value of the applied angular velocity.
 14. The method according to claim 13, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 15. The method according to claim 13, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 16. A piezoelectric generating element comprising: a substrate having a vibration part; and a piezoelectric film bonded to the vibration part and having a piezoelectric layer sandwiched between a first electrode and a second electrode, wherein the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; and α represents a value of not less than 0.20 and not more than 0.50.
 17. The piezoelectric generating element according to claim 16, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 18. The piezoelectric generating element according to claim 16, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn.
 19. A method of generating electric power using a piezoelectric generating element, the method comprising: a step (a) of preparing the piezoelectric generating element, wherein the piezoelectric generating element comprises: a substrate having a vibration part; and a piezoelectric film bonded to the vibration part and having a piezoelectric layer sandwiched between a first electrode and a second electrode, the first electrode comprises a Na_(x)M_(1-x) layer having a (001) orientation only; the piezoelectric layer is a (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer having a (001) orientation only; the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is formed on the Na_(x)M_(1-x) layer; M represents Pt, Ir, or PtIr; Q represents Fe, Co, Zn_(0.5)Ti_(0.5), or Mg_(0.5)Ti_(0.5); x represents a value of not less than 0.002 and not more than 0.02; and α represents a value of not less than 0.20 and not more than 0.50; and a step (b) of vibrating the vibration part to obtain electric power through the first electrode and the second electrode.
 20. The method according to claim 19, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer is in contact with the Na_(x)M_(1-x) layer.
 21. The method according to claim 19, wherein the (1-α) (Bi, Na, Ba) TiO₃-αBiQO₃ layer further contains Mn. 